U.S. patent application number 10/071764 was filed with the patent office on 2003-06-19 for chemiluminescent composition for emitting red light.
Invention is credited to Baek, Jong Hoon, Kim, Yong Fan, Kim, Yong Rai, Park, Koon Ha.
Application Number | 20030111649 10/071764 |
Document ID | / |
Family ID | 19715305 |
Filed Date | 2003-06-19 |
United States Patent
Application |
20030111649 |
Kind Code |
A1 |
Park, Koon Ha ; et
al. |
June 19, 2003 |
Chemiluminescent composition for emitting red light
Abstract
The present invention discloses a chemiluminescent composition
generating red light comprising a solvent, an oxalate compound and
a perylene compound represented by the following formula 2: 1 (in
which, R is a C.sub.12-C.sub.20 alkyl group), wherein the perylene
compound is present in the composition in an amount of 0.1 to 0.5%
by weight, based on the total composition.
Inventors: |
Park, Koon Ha;
(Daejeon-City, KR) ; Kim, Yong Rai; (Sungnam-City,
KR) ; Kim, Yong Fan; (Gongju-City, KR) ; Baek,
Jong Hoon; (Suwon-City, KR) |
Correspondence
Address: |
Daniel F. Drexler
55 Griffin South Road
Bloomfield
CT
06002
US
|
Family ID: |
19715305 |
Appl. No.: |
10/071764 |
Filed: |
February 7, 2002 |
Current U.S.
Class: |
252/700 |
Current CPC
Class: |
C07D 471/06 20130101;
C09K 11/06 20130101 |
Class at
Publication: |
252/700 |
International
Class: |
C09K 003/00 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 22, 2001 |
KR |
2001-65156 |
Claims
What is claimed is:
1. A chemiluminescent composition emitting red light comprising a
solvent, an oxalate compound and a perylene compound represented by
the following formula 2: 7in which, R is a C.sub.12-C.sub.20 alkyl
group, wherein the perylene compound is present in the composition
in an amount of 0.1 to 0.5% by weight, based on the total
composition.
2. The chemiluminescent composition as set forth in claim 1,
wherein the perylene compound represented by formula 2 is selected
from the group consisting of
N,N'-didodecyl-1,6,7,12-tetrakis(4-t-butylphenoxy)-3,4,9,10-
-perylene tetracarboxdiimide,
N,N'-dihexadecyl-1,6,7,12-tetrakis(4-t-butyl-
phenoxy)-3,4,9,10-perylenetetracarboxdiimide, and
N,N'-dioctadecyl-1,6,7,1-
2-tetrakis(4-t-butylphenoxy)-3,4,9,10-perylenetetracarboxdiimide.
3. The chemiluminescent composition as set forth in claim 1,
wherein the oxalate compound is
bis(2,4,5-trichloro-6-carbopentoxyphenyl)oxalate.
4. The chemiluminescent composition as set forth in claim 1,
wherein the oxalate compound is present in the composition in an
amount of 5 to 18% by weight, based on the total composition.
5. The chemiluminescent composition as set forth in claim 1,
wherein the solvent is selected from the group consisting of
dibutyl phthalate, dibutyl benzoate and mixtures thereof.
6. A chemiluminescent composition comprising a solvent, an oxalate
compound, a perylene compound represented by the following formula
2, and a peroxide component: 8in which, R is a C.sub.12-C.sub.20
alkyl group, wherein the perylene compound is present in the
composition in an amount of 0.1 to 0.5% by weight, based on the
total composition.
7. The chemiluminescent composition as set forth in claim 6,
wherein the peroxide component is included in a solution form in
the composition.
8. The chemiluminescent composition as set forth in claim 7,
wherein the solution of the peroxide component includes the
peroxide in an amount of 1 to 5% by weight, based on the
solution.
9. The chemiluminescent composition as set forth in claim 7,
wherein the solution of the peroxide component contains a
solvent.
10. The chemiluminescent composition as set forth in claim 9,
wherein the solvent is selected from the group consisting of
dibutyl phthalate, dimethyl phthalate, dibutyl benzolate, and
mixtures comprising at least one of foregoing.
11. The chemiluminescent composition as set forth in claim 7,
wherein the solution including the peroxide component contains a
catalyst.
12. The chemiluminescent composition as set forth in claim 11,
wherein the catalyst is salicylate.
13. The chemiluminescent composition as set forth in claim 11,
wherein the catalyst is contained in an amount of 0.001 to 0.05% by
weight, based on the total solution of the peroxide component.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a chemiluminescent
composition, and more particularly to a chemiluminescent
composition for emitting red light which exhibits higher intensity
and longer lifetime of light than conventional chemiluminescent
compositions emitting red light.
[0003] 2. Description of the Related Art
[0004] Red color is generally used for safety and rescue purposes.
Thus, there exists a significant demand for chemiluminescent
products generating red light. The chemiluminescent products
generating such a red light have an intensity and afterglow
duration which might be dependent on a fluorescent dye therein.
[0005] As fluorescent dyes providing red light, there are known
several compounds, which can be generally caused to generate
chemiluminescence by a reaction between an oxalate compound and a
peroxide component with the dye.
[0006] U.S. Pat. No. 3,557,233 discloses the use of derivatives of
aromatic compounds (such as naphthacene, tetracene and the like),
which are substituted by a phenylethynyl group, as a fluorescent
dye providing red light. However, the fluorescent dye disclosed in
the above patent has an unsatisfactory light intensity and
afterglow duration.
[0007] Accordingly, recently, the use of perylenetetracarboxdiimide
compound as a dye for oxalate chemiluminescent products is
disclosed.
[0008] In particular, U.S. Pat. No. 4,845,223 provides a
perylenetetracarboxdiimide compound represented by the following
formula 1. 2
[0009] Wherein, R.sup.1 and R.sup.2 are identical or different, and
independently selected from a group consisting of aliphatic, cyclic
aliphatic, aromatic, and cyclic aromatic radicals, and X, Y, and Z
independently represent chlorine, bromine or OR.sup.3, wherein
R.sup.3 is a substituted or unsubstituted phenyl, naphthyl or
anthryl group.
[0010] Unfortunately, where a perylenetetracarboxdiimide compound
represented by formula 1 is used for chemiluminescent compositions,
the most serious problem raised is low solubility in a solvent. In
other words, owing to low solubility of the
perylenetetracarboxdiimide compound in dibutyl phthalate or
dimethyl phthalate, which are generally used as a solvent for
chemiluminescent compositions, there are problems in that the
initial light intensity is low and the afterglow duration is
short.
[0011] Accordingly, recent technical developments have been
directed toward increasing the solubility of
perylenetetracarboxdiimide dye in the above solvents to increase
the initial intensity of chemiluminescent light.
[0012] As one of such technologies, U.S. Pat. No. 5,122,306
discloses the use of a perylene compound for producing a
chemiluminescent composition, which perylene compound is
represented by the above formula 1, wherein R.sup.1 and R.sup.2 are
identical, and are a substituted or unsubstituted C.sub.1-C.sub.6
alkyl or phenyl radical, and each of X, Y, and Z is OR.sup.3,
wherein R.sup.3 is a substituted or unsubstituted phenyl group.
More particularly, the U.S. patent provides a chemiluminescent
composition comprising a perylene compound of the structure
described above, a solvent, and an oxalate compound and a method
for obtaining a red chemiluminescent light by mixing a solution
containing a peroxide component with the composition.
[0013] The technology disclosed in U.S. Pat. No. 5,122,306 has an
advantage in that the initial intensity and afterglow duration of
chemiluminescent light are greatly enhanced by remarkably
increasing the solubility of a perylene compound to a solvent, in
comparison with conventionally used perylene compounds. However, it
also has disadvantages in that the initial intensity of
chemiluminescent light is still low. In a chemiluminescent product,
the most important thing is the initial intensity up to 2 hours.
Strong initial intensity and stable duration are the desirable
requirements for products that can be used for longer than 24
hours.
SUMMARY OF THE INVENTION
[0014] Therefore, the present invention has been made in view of
the above problems, and it is an object of the present invention to
provide a chemiluminescent composition emitting red light, which
has very high initial intensity of light and particularly, is
applicable to products requiring chemiluminescence lasting more
than 24 hours.
[0015] It is another object of the present invention to provide a
chemiluminescent composition in solution form.
[0016] In accordance with one aspect of the present invention,
there is provided a chemiluminescent composition generating red
chemiluminescence, which comprises a solvent, an oxalate compound
and a perylene compound, in which the perylene compound is one
represented by formula 2 and present in the composition in an
amount of 0.1 to 0.5% by weight, based on the total composition.
3
[0017] Wherein, R is a C.sub.12-C.sub.20 alkyl group.
[0018] In accordance with another aspect of the present invention,
there is provided a chemiluminescent composition containing a
solution including a peroxide component and the chemiluminescent
composition.
[0019] The above and other objects, features and other advantages
of the present invention will be more clearly understood from the
following detailed description.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0020] The present invention pertains to a chemiluminescent
composition generating red chemiluminescent light, which comprises
a solvent, an oxalate compound and a perylene compound represented
by formula 2. The chemiluminescent composition generates red
chemiluminescence by reaction with a peroxide component.
[0021] In the perylene compound represented by formula 2, R is a
C.sub.12-C.sub.20 alkyl group. In particular, R is preferably a
linear alkyl group. The perylene compound having such a long carbon
chain alkyl group has much higher initial intensity of
chemiluminescent light and higher solubility than conventional
perylene compounds, thereby enabling the perylene compound to be
used for products requiring long lasting chemiluminescence.
[0022] More preferably, the perylene compound of formula 2 is
selected from a group consisting of
N,N'-didodecyl-1,6,7,12-tetrakis(4-t-butylphen-
oxy)-3,4,9,10-perylenetetracarboxdiimide, wherein R is a C.sub.12
dodecyl group;
N,N'-dihexadecyl-1,6,7,12-tetrakis(4-t-butylphenoxy)-3,4,9,10-pery-
lenetetracarboxdiimide, wherein R is a C.sub.16 hexadecyl group;
and
N,N'-dioctadecyl-1,6,7,12-tetrakis(4-t-butylphenoxy)-3,4,9,10-perylenetet-
racarboxdiimide, wherein R is a C.sub.18 octadecyl group.
[0023] The perylene compound represented by formula 2 can be
synthesized according to conventional processes for providing
perylene compounds.
[0024] For example, the perylene compound of formula 2 can be
obtained easily according to the process as follows;
Perylene-3,4,9,10-tetracarbox- ylic acid dianhydride represented by
the following formula 3, an amine compound represented by formula
4, acetic acid and 1-methyl-2-pyrrolidone were mixed under nitrogen
atmosphere. The reaction mixture was heated to 90.degree. C. and
stirred for six hours. Then, the reaction mixture was cooled to
room temperature, stirred for another one hour. The liquid phase
was filtered off by suction to yield a solid. The obtained solid
was added to aqueous 10% KOH solution, heated to 70.degree. C. and
stirred for 30 minutes. The solution was cooled to room temperature
and suctioned off again. The residue was washed with excess water
and methanol, and dried to obtain a compound represented by formula
5. The obtained compound of formula 5 was refluxed in chloroform
for 8 hours while injecting Cl.sub.2 gas. Then, the resulting
reaction solution was cooled to room temperature and stirred for 24
hours while feeding air. The solution was then washed twice with
saturated aqueous K.sub.2CO.sub.3 solution, and the solvent was
distilled off under a reduced pressure. The residue was
recrystallized from 1,2-dichloroethane to afford an orange solid
represented by formula 6 was obtained. Then, a mixture of the
obtained compound of formula 6, 4-t-butylphenol, anhydrous
K.sub.2CO.sub.3 and 1-methyl-2-pyrrolidinone was stirred for 8
hours at 120.degree. C. under nitrogen atmosphere. After cooling to
room temperature, the reaction mixture was stirred for one hour and
filtered. The solid obtained was added to distilled water and
stirred for 2 hours at room temperature. Then, the liquid phase was
suctioned off again, washed with distilled water and methanol, in
order, and dried, by which the perylene compound represented by
formula 2 was obtained. 4 NH.sub.2--R [formula 4]
[0025] Wherein, R is a C.sub.12-C.sub.20 alkyl group. 5
[0026] Wherein, R is a C.sub.12-C.sub.20 alkyl group. 6
[0027] Wherein, R is a C.sub.12-C.sub.20 alkyl group.
[0028] The perylene compound of formula 2 is present in the
composition according to the present invention in an amount of,
preferably 0.05 to 0.5% by weight, based on the total composition.
Where the perylene compound is present in an amount of less than
0.05% by weight, based on the total composition, there is a problem
in that the generated light is poor in intensity and duration.
Where the perylene compound is present in an amount of more than
0.5%, the perylene compound may be precipitated as a solid.
Accordingly, it is preferable that the perylene compound is
contained in the prescribed range.
[0029] The chemiluminescent composition containing the perylene
compound represented by formula 2 also comprises a solvent. The
solvent can be selected among common solvents. According to the
present invention, the solvent may be one or more selected from a
group consisting of tertiary alcohols, dibutyl phthalate and
dibutyl benzoate.
[0030] The chemiluminescent composition according to the present
invention also includes an oxalate compound. Preferably,
bis(2,4,5-trichloro-6-carb- opentoxyphenyl)oxalate may be used as
the oxalate compound.
[0031] According to the invention, the oxalate compound is present
in the composition in an amount of 5 to 18% by weight, based on the
total composition. Where the oxalate compound is present in an
amount of less than 5.0% by weight, based on the total composition,
the intensity of light will be very low. Where the oxalate compound
present in an amount of more than 18%, there will be a problem in
that the oxalate compound is precipitated as a solid. Accordingly,
it is preferable that the oxalate compound is contained in the
prescribed range.
[0032] The chemiluminescent composition according to the present
invention generates red chemiluminescence by reaction with a
peroxide component. Thus, in another aspect of the present
invention, it also pertains to a chemiluminescent solution
containing the chemiluminescent composition and a solution
including a peroxide component. As the solution including a
peroxide component, the one that is commonly used in the art can be
used.
[0033] It is preferable that the solution including a peroxide
component contains the peroxide component in an amount of 0.5 to 5%
by weight, based on the total solution. Where the peroxide
component is present in the solution in an amount of less than 0.5%
by weight, based on the total solution, the initial
chemiluminescence will be weak. Where the peroxide component is
present in an amount of more than 5%, the intensity of initial
chemiluminescent light is so high that the duration of
chemiluminescence is shorter. Accordingly, it is preferable that
the peroxide component is present in the prescribed range. The
peroxide component can be hydrogen peroxide, percarboxylic acid and
the like, preferably hydrogen peroxide in view of reactivity.
[0034] The solution including the peroxide component also includes
a solvent. According to the present invention, the solvent is one
or more selected from a group consisting of tertiary alcohol,
dimethyl phthalate, dibutyl phthalate and dibutyl benzoate.
[0035] Further, the solution including the peroxide component may
include a catalyst. In the present invention, salicylate may be
used as the catalyst. The catalyst is preferably present in the
solution in an amount of 0.01 to 0.05% by weight, based on the
total solution.
[0036] Preferably, the chemiluminescent composition and the
solution including the peroxide component are mixed in a ratio of
1:1 to 5:1. Where the ratio of the chemiluminescent composition to
the solution including the peroxide component is less than 1:1, the
duration of chemiluminescence will be shorter. Where the ratio of
the chemiluminescent composition to the solution including the
peroxide component is more than 5:1, the initial chemiluminescence
is weak. Accordingly, it is preferable that the chemiluminescent
composition and the solution including the peroxide component are
mixed in the prescribed range.
[0037] When the solution including the peroxide component formed as
above is mixed with the chemiluminescent composition of the
invention in the prescribed ratio, the red chemiluminescence lasts
for more than 48 hours, and the afterglow lasts for more than 60
hours.
[0038] The chemiluminescent light generated by the present
composition can be used in common application fields, for example,
for signaling, decoration, games, hunting, fishing or military
purposes, as are well known. The chemiluminescent composition also
can generate variously colored light by mixing with other
fluorescent dyes or ordinary dye. For example, pink
chemiluminescent light can be obtained by mixing with a blue
fluorescent dye.
[0039] Now, preferred embodiments of the present invention will be
described in more detail. The following preferred embodiments are
described only for a better understanding of the present invention,
and are not intended to limit the invention.
EXAMPLE 1
[0040] 13.5 g of bis(2,4,5-trichloro-6-carbopentoxyphenyl)oxalate
and 86.4 g of dibutyl phthalate were introduced to a flask, heated
to 120.degree. C. under nitrogen atmosphere while stirring. Then,
0.100 g of
N,N'-didodecyl-1,6,7,12-tetrakis(4-t-butylphenoxy)-3,4,9,10-perylenetetra-
carboxdiimide was added to the mixture, stirred thoroughly, and
cooled to room temperature, by which a chemiluminescent composition
was obtained.
EXAMPLE 2
[0041] The procedure of Example 1 was repeated using equivalent
molar amounts of
N,N'-dihexadecyl-1,6,7,12-tetrakis(4-t-butylphenoxy)-3,4,9,10--
perylenetetracarboxdiimide (0.108 g) instead of
N,N'-didodecyl-1,6,7,12-te-
trakis(4-t-butylphenoxy)-3,4,9,10-perylenetetracarboxdiimide, by
which a chemiluminescent composition was obtained.
EXAMPLE 3
[0042] The procedure of Example 1 was repeated using equivalent
molar amounts of
N,N'-dioctadecyl-1,6,7,12-tetrakis(4-t-butylphenoxy)-3,4,9,10--
perylenetetracarboxdiimide (0.113 g) instead of
N,N'-didodecyl-1,6,7,12-te-
trakis(4-t-butylphenoxy)-3,4,9,10-perylenetetracarboxdiimide, by
which a chemiluminescent composition was obtained.
COMPARISON 1
[0043] The procedure of Example 1 was repeated using equivalent
molar amounts of
N,N'-dibutyl-1,6,7,12-tetrakis(4-t-butylphenoxy)-3,4,9,10-pery-
lenetetracarboxdiimide (0.083 g) instead of
N,N'-didodecyl-1,6,7,12-tetrak-
is(4-t-butylphenoxy)-3,4,9,10-perylenetetracarboxdiimide, by which
a chemiluminescent composition was obtained.
EXPERIMENT 1
[0044] To 4.0 g of 60% hydrogen peroxide was added a solution of
dimethyl phthalate and t-butyl alcohol (4:1) to a total weight of
100 g. 0.018 g of salicylate was added to the solution to produce a
solution including a peroxide component. The obtained solution was
mixed with each of chemiluminescent compositions produced from
Example 1-3 and Comparison 1 in a ratio of 1:3, and the intensity
of light generated was measured at predetermined time intervals by
a powermeter (from Coherent Co.; model No.: FM) while all outside
light was excluded in a box 28 cm.times.25 cm.times.13 cm in size.
The results are summarized in Table 1.
1 TABLE 1 Light intensity (nw) according to time (hr) 0.51 1 2 3 4
6 8 10 12 24 48 Example 1 873 667 549 443 370 267 201 158 115 59 25
Example 2 822 622 525 413 340 262 191 158 125 76 33 Example 3 716
569 491 397 310 227 175 148 116 68 31 Comparison 1 478 429 414 350
300 215 169 136 112 64 27
EXPERIMENT 2
[0045] To 4.0 g of 60% hydrogen peroxide was added a solution of
dimethyl phthalate and t-butyl alcohol (4:1) to a total weight of
100 g. 0.018 g of salicylate was added to the solution to produce a
solution including a peroxide component. The obtained solution was
mixed with each of chemiluminescent compositions produced from
Example 1-3 and Comparison 1 in a ratio of 1.6:2.4, and the
intensity of light generated was measured at predetermined time
intervals by a powermeter (from Coherent Co.; model No.: FM) while
all outside light was excluded in a box of 28 cm.times.25
cm.times.13 cm in size. The results are summarized in following
Table 2.
2 TABLE 2 Light Intensity (nw) according to time (hr) 0.5 1 2 3 4 6
8 10 12 24 48 Example 1 864 688 560 440 331 240 163 118 81 25 5
Example 2 810 643 539 429 330 227 161 111 79 24 5 Example 3 789 642
531 420 323 222 153 113 81 25 5 Comparison 1 716 631 552 442 352
239 168 121 87 28 6
EXPERIMENT 3
[0046] To 4.0 g of 60% hydrogen peroxide was added a solution of
dimethyl phthalate and t-butyl alcohol (4:1) to a total weight of
100 g. 0.018 g of salicylate was added to the solution to produce a
solution including a peroxide component. The obtained solution was
mixed with each of chemiluminescent compositions produced from
Example 1-3 and Comparison 1 in a ratio of 1.7:2.6, and the
intensity of light generated was measured at predetermined time
intervals by a powermeter (from Coherent Co.; model No.: FM) while
all outside light was excluded in a box of 28 cm.times.25
cm.times.13 cm in size. The results are summarized in following
Table 3.
3 TABLE 3 Light Intensity (nw) according to time (hr) 0.5 1 2 3 4 6
8 10 12 24 48 Example 1 844 657 480 403 361 261 192 142 113 45 29
Example 2 773 641 459 374 367 284 220 184 143 58 33 Example 3 745
580 500 364 359 263 206 146 113 47 31 Comparison 1 587 498 422 377
358 283 231 165 132 55 30
[0047] As shown from the Table 1 to Table 3, it is found that
chemiluminescent compositions formed according to the invention,
respectively, are superior to conventional chemiluminescent
compositions in view of the initial light intensity and afterglow
duration, as a result of measuring light intensity while varying
the mixing ratio of each of chemiluminescent compositions and a
solution including a peroxide component.
[0048] As described above, the present invention can provide a
chemiluminescent composition, which has excellent stability
compared with conventional chemiluminescent compositions generating
red light, and which has strong initial light intensity and long
afterglow duration, and a chemiluminescent solution based on the
composition.
* * * * *